42052-52-8Relevant academic research and scientific papers
Experimental evidence for chair-like transition states in aldol reactions of methyl ketone lithium enolates: Stereoselective synthesis and utilization of a deuterium-labeled enolate as a probe of reaction stereochemistry
Liu, Christopher M.,Smith III, William J.,Gustin, Darin J.,Roush, William R.
, p. 5770 - 5771 (2005)
Aldol reactions of methyl ketone lithium enolates proceed via chairlike Zimmerman-Traxler transition states with 7:1 to 50:1 preference over alternative, boatlike transition structures, as determined by studies involving the configurationally stable deute
Large rate accelerations in aldol reaction of ortho-substituted benzaldehydes
Das, Goutam,Thornton, Edward R.
, p. 5239 - 5242 (1991)
The relative reactivities of ortho- and para-substituted benzaldehydes with the dibutylboron enolate of pinacolone have very different substituent dependences; ortho substituents give large rate enhancements with electron-releasing substituents, while para substituents give extremely small rate effects. Since chelation is inaccessible to the boron enolate (which must also complex to the aldehyde), the origin of the large ortho effects was investigated by multiple regression analysis, which shows that the rates are insensitive to steric effects, but are dominated by resonance interactions. The polarizability and, to a small extent, the field effect of the substituents also affect the reactivity. The most consistent mechanistic explanation involves a variable transition structure with the relative degrees of aldehyde (Chemical Equation Presented) bond-breaking and enolate-aldehyde C...C bond-making changing with substituents.
One-pot enol silane formation-Mukaiyama aldol reactions: Crossed aldehyde-aldehyde coupling, thioester substrates, and reactions in ester solvents
Downey, C. Wade,Dixon, Grant J.,Ingersoll, Jared A.,Fuller, Claire N.,MacCormac, Kenneth W.,Takashima, Anna,Sediqui, Rohina
, (2019/10/14)
Trimethylsilyl trifluoromethanesulfonate (TMSOTf) and a trialkylamine base promote both in situ enol silane/silyl ketene acetal formation and Mukaiyama aldol addition reactions between a variety of reaction partners in a single reaction flask. Isolation of the required enol silane or silyl ketene acetal is not necessary. For example, crossed aldol reactions between α-disubstituted aldehydes and non-enolizable aldehydes yield β-hydroxy aldehydes in good yield. In a related reaction, the common laboratory solvent ethyl acetate functions as both an enolate precursor and a green reaction solvent. When thioesters are employed as enolate precursors, high yields for additions to non-enolizable aldehydes are routinely observed.
Method for preparing organoboron compound and beta-hydroxy compound by supported copper ion Y type molecular sieve catalyst
-
, (2019/01/15)
The invention relates to a method for preparing an organoboron compound and a beta-hydroxy compound by a supported copper ion Y type molecular sieve catalyst. The method for preparing the organoboroncompound mainly comprises the following steps: the step
Methods of preparing organic boron compound and beta-carbonyl compound by catalyzing copper ion loaded chitosan microspheres
-
Paragraph 0177-0183, (2018/03/09)
The invention relates to methods of preparing an organic boron compound and a beta-carbonyl compound by catalyzing copper ion loaded chitosan microspheres. The preparation method of the organic boroncompound mainly comprises the following steps of A, addi
Sml2-promoted reformatsky-type coupling reactions in exceptionally hindered contexts
Sparling, Brian A.,Moslin, Ryan M.,Jamison, Timothy F.
supporting information; experimental part, p. 1291 - 1294 (2009/04/08)
Highly substituted, very hindered enones were synthesized using a two-step procedure that utilizes a diiodosamarium-promoted Reformatsky-type coupling and dehydration using Martin sulfurane. Both α-chloro- and α-bromoketones were coupled with a variety of carbonyl nucleophiles to form the intermediate β-hydroxyketones, occurring with excellent diastereoselectivity, favoring the syn isomer (R1 = Me). This technique complements other methods and enables the preparation of enones outside of the scope of current olefination methodology.
Organotin perfluorooctanesulfonates as air-stable Lewis acid catalysts: Synthesis, characterization, and catalysis
An, De Lie,Peng, Zhihong,Orita, Akihiro,Kurita, Akinobu,Man-E, Sumiyo,Ohkubo, Kei,Li, Xingshu,Fukuzumi, Shunichi,Otera, Junzo
, p. 1642 - 1647 (2007/10/03)
The reactions of 1,3-dichloro-1,1,3,3-tetrabutyldistannoxane and di-alkyltin dihalides with silver perfluoro-octanesulfonate provided the corresponding sulfonates as hydrates. The number of water molecules (n) of hydration was dependent on the conditions. The distannoxane derivative was identified as n from 0.5 to 6, while in the hydrated mononuclear species and DMSO complexes n varied widely from 4 to 13. 119Sn NMR spectroscopy and conductivity measurements indicated the ionic dissociation of these compounds in solution. These compounds exhibited unusually high solubility in polar organic solvents. The ionic dissociation together with facile hydration probably causes the unusual solubility. The Lewis acidity of these compounds was found to be high among organotin derivatives on the basis of ESR spectra of Superoxide/ metal-ion complexes. In contrast to well-known organotin Inflates, these compounds suffered no hydrolysis upon storage in open air. The high catalytic activity of the distannoxane 1 was exemplified for various carboncarbon bond-forming reactions, such as Mukaiyama-aldol as well as -Michael reactions and allylation of aldehydes.
Decarboxylative aldol reactions of allyl β-keto Esters via heterobimetallic catalysis
Lou, Sha,Westbrook, John A.,Schaus, Scott E.
, p. 11440 - 11441 (2007/10/03)
Mild and selective heterobimetallic-catalyzed decarboxylative aldol reactions involving allyl β-keto esters have been developed. The reaction is promoted by Pd(0)- and Yb(III)-DIOP complexes at room temperature and involves the in situ formation of a ketone enolate from allyl β-keto esters followed by addition of the enolate to aldehydes. The reaction is a new example of heterobimetallic catalysis in which the optimized reaction conditions require the addition of both metals. Copyright
Albumin-controlled stereoselective reduction of 1,3-diketones to anti-diols
Benedetti, Fabio,Berti, Federico,Donati, Ivan,Fregonese, Massimo
, p. 828 - 829 (2007/10/03)
An unprecedented combination of high chemo- and stereoselectivity in the NaBH4 reduction of 1:1 complexes between albumin and aromatic 1,3-diketones results in the formation of anti 1,3-diols with de up to 96%.
Reformatsky-type reaction of α-haloketones promoted by titanium tetraiodide
Shimizu, Makoto,Kobayashi, Fumiko,Hayakawa, Ryuuichirou
, p. 9591 - 9595 (2007/10/03)
Titanium(IV) tetraiodide induces a Reformatsky-type reaction of α-iodoketones with carbonyl compounds to give β-hydroxy ketones in good to high yields.
